New water-insoluble azo-compounds containing a carboxamido-carbostyril group

ABSTRACT

Water insoluble azo dyestuff pigments of the formula

United States Patent Mueller 1 NEW WATER-INSOLUBLE AZO- COMPOUNDSCONTAINING A CARBOXAMIDO-CARBOSTYRIL GROUP [72] Inventor: Willy Mueller,Fuerfelderstrasse 55,

Riehen, Switzerland [22] Filed: Sept. 3, 1959 [21] Appl. No.: 855,028

[30] Foreign Application Priority Data Sept. 5, 1969 Switzerland..13326/68 [56] References Cited UNITED STATES PATENTS 2,754,293 7/1956Brody et a1. 2Q/155 [151 3,684,792 [451 Aug. 15, 1972 2,781,345 2/1957Leavitt et a1 ..260/ 155 X 3,137,685 6/1964 Buckley et al ..260/1553,532,520 10/ 1970 Dawson et a1. ..260/155 X Primary Examiner-Floyd D.Higel Attorneyl-larry Goldsmith, Joseph G. Kolodny and Mario A. Monaco[57] ABSTRACT Water insoluble azo dyestufl pigments of the formula R,-N-N-R,CONHR 1 in which R, represents an aromatic or heterocyclic residue,R is a hydroxynaphthalene residue, in which the azo, hydroxyl andcarboxylic acid amide groups are in the 1,2,3-positions, or R,represents the residue of an enolisable or enolised ketomethylenecompound, and R represents a carbostyril residue. They are useful forcoloring laqueurs and plastic masses in yellow to red shades fast tolight and migration.

7 Claims, No Drawings NEW WATER-INSOLUBLE AZO-COMPOUNDS CONTAINING ACARBOXAMIDO-CARBOSTYRIL GROUP The present invention provides valuablewater-insoluble azo dyestuff pigments of the general formula the azo,hydroxyl and carboxylic acid amide groups are in the 1, 2, 3positions,or R represents the residue of an enolisable or enolised ketomethylenecompound, and R represents a carbostyril residue.

The present invention also provides a process for preparing thewater-insoluble azo dyestuff pigments of the general formula 1, whichcomprises a. condensing a carboxylic acid halide of the formula in whichR, and R have the meanings given above and Hal represents a halogenatom, with an amino-carbostyril, or

b. coupling a diazoor diazo-arninocompound of an amine of the formulawhereR has the meaning given above, with a coupling component of theformula in which R and R have the meanings given above.

As the dyestuffs of the invention are pigments, it will be understoodthat groups imparting solubility in water, especially acid groupsimparting solubility in water, for example, sulphonic acid or carboxylicacid groups, are excluded as substituents.

Of special interest are dyestuffs of the formula CONHR3 in which Rrepresents a benzene residue, R represents a carbostyril residue, and Yrepresents a hydrogen or halogen atom or an alkoxy, nitro or cyanogroup. These dyestuffs preferably correspond to the formula 'in which Wrepresents a halogen atom or an alkyl, alkoxy, phenoxy, nitro orcarboxylic acid ester group, U

or trifluoromethyl, and V represents hydrogen, chloro,

bromo, methyl, nitro, methoxy, C carbalkoxy, carbophenoxy, carboxamido,N-C alkyl carboxamido, trifluoromethyl, unsubstituted carboxylicphenylamido, substituted carboxylic phenylamido wherein thesubstitutents are selected from the group consisting of chloro, methyl,phenyl and trifluoromethyl; sulfonamido, sulfonic ethylamido, sulfonicphenylamido, substituted sulfonic phenylamido wherein the sub? stituentsare selected from the group consisting of chloro and trifluoromethyl. Xrepresents a hydrogen atom or an alkyl or phenyl group, X and X eachrepresents a hydrogen or halogen atom or an alkyl, phenyl or alkoxygroup, and Y has the meaning given above, and in which the NH-group isbound in the 6- or 7-position of the carbostyril residue.

Also of interest are the dyestufis of the formula in which R,-,, R U, V,W, X X and X have the meanings given above, or those of the formulaCOOHs COOHs RaNHCOCH-N=NR5N==NH-CONHRa and especially those of theformula COCHs in which R represents a diphenyl residue, 2, and Z eachrepresents a hydrogen or halogen atom or an alkyl or alkoxy group, and RX X and X have the meanings given above.

The dyestuffs of the formula (2) are advantageously obtained bycondensing an azo-dyestuff-carboxylic acid chloride of the formula Q-OHY O0OH As examples of diazotisable amines of the formula R NH there maybe mentioned the following:

Aniline and especially halogenated anilines, such as 2-, 3- or4-chloraniline,

2,4-dichloraniline,

2,3-dichloraniline, 2,5-dichloraniline, 3,4-dichloraniline,2,6-dichloraniline, 2,4,5-trichloraniline, 2,4,6-trichloraniline, 2-, 3-or 4-bromaniline, 2,4-dibromaniline, 2,5-dibromaniline, 2-fluoraniline,2-methyl-3-chloraniline 2-methyl-4-chloraniline,Z-methyl-S-chloraniline, 3-trifluoromethylaniline,3,5-di-trifluoromethylaniline, 2-chloro-S-trifluoromethylaniline,4-chloro-2-trifluoromethylaniline, 4-chloro-3-trifluoromethylaniline,2-methoxy-5-trifluoromethylaniline, and also nitranilines, such as 2-,3- or 4-nitraniline, 2,4-dinitraniline, 4-chloro-2-nitraniline,2-chloro-4-nitraniline, 2,5-dichloro-4-nitraniline,4-methyl-3-nitraniline, 4-methyl-2-nitraniline, Z-methyl-S-nitraniline,2-methyl-4-nitraniline, 2,4-dimethyl-3-nitraniline, and also alkoxyandphenoxy-anilines, such as 2- and 4-methoxyaniline, 2- and4-ethoxyaniline,

lide,

4 2,4-dirnethoxyaniline, 2,5-dimethoxyaniline, Z-methoxy-S-chloraniline,2-methoxy-5-nitraniline, 3-chloro-4-methoxyaniline,2-methoxy-4-nitraniline, 2-nitro-4-methoxyaniline,2-nitro-5-methoxyaniline, 2-nitro-4-ethoxyaniline,5-nitro-4-methyl-2-methoxyaniline, 2-methoxy-4-chloro-5 -methylaniline,2,4-dimethoxy5-chloraniline, 2,5-dimethoxy-4-chloraniline,2-amino-4-chlorodiphenyl ether, 2-amino-2' 4-dichlorodiphenyl ether,2-amino 4,4'-dichlorodiphenyl ether, 2-amino-4-trifluoromethyl-diphenylether, 2-amino-4-trifluoromethyl-4'-chlorodiphenyl ether,4-amino-2-trifluoromethyl-diphenyl ether, and also4-amino-3-nitrobenzotrifluoride, Z-amino-S-nitrobenzotrifiuoride,2-amino-benzoic acid methyl ester, Z-amino-benzoic acid ethyl ester,4-chloro-3-aminobenzoic acid methyl ester, 4-methyl-3-aminobenzoic acidethyl ester, 4-methoxy-3-aminobenzoic acid methyl ester,Z-amino-S-nitro-benzoic acid methyl ester, 3-amino-benzoic acid phenylester, 4-amino-benzoic acid phenyl ester, 4-amino-4'-diphenyl-carboxylicacid ethyl ester, Z-aminO-diphenyl sulphone, 4-methoxy-3-aminobenzenel-benzyl sulphone, 4-methoxy-3-aminobenzenel -ethyl sulphone, and also3-amino-benzoic acid amide, 4-amino-benzoic acid amide,4-chloro-3-aminobenzoic acid amide, 4-methyl-3-aminobenzoic acid amide,4-methyl-3-amino-benzoic acid-N-methylamide, 4-methyl-3-aminobenzoicacid-N-diethylamide, 4-amino-3-methylbenzoic acid amide,4-methoxy-3-amino-benzoic acid amide, 4-methoxy-3-amino-benzoicacid-N-methylamide, 4-chloro-3-amino-benzoic acid anilide,4-chloro-3-amino-benzoic acid-4'-chloranilide, 4-chloro-3-amino-benzoicacid-2' ,4'-dichloranilide, 4-chloro-3-amino-benzoic acid-2' ,4 ,5-trichloranilide,

4-chloro-3-amino-benzoic acid-3'- trifluoromethylanilide,

4-chloro 3-amino-benzoic acid-2 '-chloro-5 trifluoromethylanilide,

lide,

2,4-dichloro-5-amino-benzoic acid-2,5'-dichlorani-2,4-dichloro-5-amino-benzoic acid-3- trifluoromethylanilide,

2,4dichloro-S-amino-benzoic acid-2 '-chloro-5 trifluoromethylanilide,

5-amino-4-methoxy-2-chloro-benzoic acid-3- trifluoromethylanilide,

4-methyl-3-amino-benzoic trifluoromethylanilide,

4methyl-3-amino-benzoic acid-3 '-chloranilide, 4-methyl-3-amino-benzoicacid-2', 4'-dichloranilide,

acid-3 4-amino-3-methyl-benzoic acid anilide, 5

4-amino-3-methyl-benzoic acid-4'-chloranilide,

4-amino-3-methyl-benzoic acid-3'- trifluoromethylanilide,

4-methoxy-3-amino-benzoic acid-3'- trifluoromethylanilide, 1O

4-methoxy-3-amino-benzoic acid-2'-chloro-5'- trifluoromethylanilide,

4-methoxy-3-amino-benzoic acid anilide, 4-methoxy-3 amino-benzoicacid-3',5'-ditrifluoromethylanilide,

4-methoxy-3-amino-benzoic lide,

4-amino-4-diphenyl-carboxylic acid anilide,4-carbomethoxy-3-amino-benzoic acid anilide,

acid-2',5'-dichlorani- 4-carbomethoxy-3-amino-benzoic acid-2,4-dichloranilide,

4-carbomethoxy-3-amino-benzoic acid-4'- methylanilide,

4-methoxy-3-arnino-benzene-sulpho-N-diethylamide,

4-methoxy-3-amino-benzene-sulphonic acid anilide,

4-methoxy-3-amino-benzene-sulphonic acid-2'5- dichloranilide,

4-chloro-3-amino-benzene-sulphonic acid anilide,

4chloro-3-amino-benzene-sulphonic acid-2'-chloro- 5'-trifluoromethylanilide.

The azo-dyestuff-carboxylic acid so obtained is treated with an agentcapable of converting a carboxylic acid into its halide, for example,chloride or bromide. Thus, there may be used, especially a phosphorushalide, for example, phosphorus pentabromide or phosphorus trichlorideor pentachloride, a phosphorus oxyhalide, and preferably thionylchloride.

The treatment with the acid halide-forming agent is advantageouslycarried out in an inert organic solvent, for example,dimethylformarnide, a chlorobenzene, for example, monoordi-chlorobenzene, toluene, xylene or nitrobenzene, and, in the case ofthe five last mentioned compounds, optionally in the presence ofdimethylformamide.

In the preparation of the carboxylic acid halides it is generally ofadvantage first to dry the azo-compound that has been produced in anaqueous medium, or to free it from water azeotropically by boiling it inan organic solvent. The azeotropic drying may, if desired, be carriedout immediately before the treatment with the acid halide-forming agent.

The azo-dyestuff-carboxylic acid chloride so obtained is then condensedwith an arnino-carbostyril, preferably one of the formula HzN OH 7 N 2 X1 As examples of amino-carbostyrils there may be mentioned thefollowing:

6-aminocarbostyril,

7-aminocarbostyril,

4-methyl-7-aminocarbostyril,

4,6-dimethyl-7-aminocarbostyril,

4,5-dimethyl-7-aminocarbostyril,

4,5 ,8-trimethyl-7-aminocarbostyril,

4-methyl-6-methoxy-7-aminocarbostyril,

4,6,8-trimethyl-7-aminocarbostyril, 4-phenyl-7-aminocarbostyril,4-methyl-6-aminocarbostyril, 4-methyl-7-chloro-6-aminocarbostyril,4-methyl-6-chloro-7-arninocarbostyril, 4,7-dimethyl-6-aminocarbostyril,4,5,8-trimethyl-6-aminocarbostyril,4-methyl-7-methoxy-6-aminocarbostyril,4-methyl-5,8-dimethoxy-6-aminocarbostyril,4-methyl-5,8-dimethoxy-6-aminocarbostyril,4-methyl-6-amino-7,8-benzo-carbostyril.

The condensation of the carboxylic acid chloride of the kind definedabove with the amino-carbostyril is advantageously carried out in ananhydrous medium at an elevated temperature, preferably in the presenceof an organic solvent, for example, toluene, monochlorobenzene,dichlorobenzene, trichlorobenzene, nitrobenzene or especiallyN-methylpyrrolidone.

An acid-binding agent, for example, anhydrous sodium acetate orpyridine, may be added. Some of the dye-stuffs obtained are crystallineand others are amorphous, and they are generally obtained in a very goodyield and in a pure state. It is of advantage first to separate the acidchloride obtained from the carboxylic acid. In some cases the separationof the acid chloride may be dispensed with without harm, and then thecondensation may immediately follow the preparation of the carboxylicacid chloride.

The dyestuffs of the formula (2) can also be obtained by coupling adiazo-compound of an amino-benzene of the formula R,,NH with a naphtholof the formula (lUNll R3 The dyestuffs of the formula (4) are obtainedadvantageously by coupling a diazotised amino-benzene with anacetoacetylamino-carbostyril, especially one of the formula OHZCOCHZCONH7 11 i suitable a very wide variety of amines, for example, aliphaticamines, for example, methylamine, ethylamine, ethanolamine, propylamine,butylamine, hexylamine and especially dimethylamine, M- -M L a. 5diethylamine, diethanolamine, methyl-ethanolamine, which 1 h 2 have then g given 9 e, Wlth dipropylamine or dibutylarnine, amino-acetic acid,thel apprtsiphzte acetoacetyl-ammo-carbostynl m the methylamino-aceticacid, butylaminoacetic acid, m0 re 0 f amino-ethane sulphonic acid,methylamino-ethane The eeuphhg 1s advantageously earned out y thesulphonic acid, guanylamino-ethane sulphonic acid, I gradual addition Ofan aqueous solution Of thfi l0 acid ajicyclic amines, for examzzrzira assssz'ziza hzzfoamassign: g c t1 S used an amount suflicient toneutralize the mineral acid i b i id, (4-sulph0phenyl)-gua nidine, 4-N-liberated from the diazonium salt during the couplingmethylamino-benzoic acid, 4-ethylamino-benzoic acid, The coupling isadvantageously carried out at a pH- 1 aminonahhthalehe 4 sulphonichgindhh zz s ggg g i j g'i z gfi sg ffggy g g isaminonaphthalene-2,4-di-sulphonic acid, heterocyclic 9 a amines, forexample, piperidine, morpholine, pyrt' AS there may be used: forfixample h 2Q rolidine, dihydroindole, and finally also sodiumcyanaespecially alkali metal salts, of formic acid, phosphoric mid: ordicyahdiamide acid or especially acetic acid. The alkaline solution ofThe diamamimmompounds so obtained are usually the coupling componentadvantageously contains a sparingly Soluble in water and ILhey can afterbeing wetting dispersing or emulsifying agent for example salted out incrystalline fdrm be separated from the an aralkyl sulphonate for exampledodecyl'benzene reaction medium. In many cases the moist press cakesulphonate or the sodium salt of 1,1 '-naphthyl-methane can be used forthe further reaction In certain cases it sulphonic acid, apolycondensation product of an alis of advantage to free the diazo amidefrom water by kylene oxide, for example, the reaction product of vacuumdrying before the reaction ethylene oxide on para-terL-octylphenol, andalso an The coupling of the diazmamhmlcompound with the alkyl f z asulpho'ncmoleate for example n'butyl naphthol is effected in an inertorganic solvent for exsulpho-rlcmoleate. The dispersion of the couplingcomample chlorobenzene orthodichlorobenzene onent ma with advanta e alscontain a r t ti olloid fo example m thylellulose or s mzl l fi g ig gehthlene yg monome y or monoe y e er, unet y ormaml e, amount of aninert organic solvent that is sparingly f ormic acid or acetic acid.When a water-miscible solfg gz aggz flg g gz ig gzfifig ?fi ggz gg ventis used it is not necessary to use the diazo-aminoexample, benzene,toluene, xylene, chlorobenzene, a f m 2 anhaidrous a i l fi P i,dichlorobenzene or nitrobenzene, or a halogenated mom ter c es may ealiphatic hydrocarbon, for example, carbon the 9 T 1 T P g. i estetrachloride or trichlorethylene, or a water-miscible 4O colup g g g ime i dd neu i organic solvent, for example, acetone, ethylene glycol sovent use l 18 ere necessary a an monomethyl ether, methyl ethyl ketone,methanol, example. hyclrogen chloride sulphur: acld fomnc ethanol,isopropanol or dimethylformamide. acld or i The coupling may also becarried out with advantage The couplmg ls preferably earned out wlth hof by continuously mixing an acid solution of the diazoniheat andadvamoageouslx, a a ZF wlthm um salt with an alkaline solution of thecoupling comrange ofgom g to an H gener y proceeds ponent in a mixingnozzle, it being of advantage to use a ga? y an P f y th b d smallexcess of the coupling component. Care should to mso u uty e plgmems so0 taupe be taken that the diazo componem and the coupling can beisolated from the reaction mixtures by filtration. component are presentin equimolecular proportions in byProducts remam m soluuon: the Plgmemsare the mixing nozzle, but a Small excess of he coupling tamed in anexcellent state of purity. In the case of pigcomponent is advantageous.This can be effected in a mems that have been obtamed h aqueous couplm?very simple manner by controlling the pHwalue of the method, anafter-treatment with organic solvents is liquid in the mixing nozzle.Attention is also paid to heeessary- Further S the Process of the hthorough stirring of the two solutions in the mixing noz- Vehhoh are the8 Ylelds ohtalhed, the favorable P 8- zle. The resulting dyestuffdispersion is continuously form of h Products e the constancy of thewithdrawn from the mixing nozzle, and the dyestufi is Properties of theP e P Separated by filt ti The pigments of the invention, owing to theirfavora- The new pigment dyestuffs can also be obtained by l P P fSuitable a e y wide e y of heating a diazo-amino-compound containing theP g p e h r for example, In h y dlspersed residue R, with the couplingcomponent in an organic form for (101011118 blah-molecular mateflhls,for examsolvent, optionally in an aqueous-organic solvent, pl Celluloseher 1' e r r polyamldes 0r polyupreferably in the presence of an acid.rethanes or polyesters, lacquers or lacquer-formers,

The aryl diazo-amides to be used in the process are solutions orproducts of acetyl-cellulose, nitrocellulose,

obtainable by methods known per se by the condensation of an aryldiazonium salt with a primary or preferably secondary amine. For thispurpose there is or natural resins or synthetic resins, such aspolymerization resins or condensation resins, for example arninoplasts,alkyd resins, phenoplasts,

polyolefines, for exa 'nble polystyrene, 4 2,4,5-trichlor- 4-me th yl ehioro 7-aminoblue-red aniline carbostyri chloride, polyethylene, Ipolypropylene, tuimmmamimbo, brown polyacrylonitnle, or rubber, casein,silicone or silicone styril resins. They can also be used with advantagein the 6 I: 9' manufacture of colored crayons, cosmetic preparations 5 7fffifi'fi brown or laminated boards. a 2,5-dichlorani The followlngExamples illustrate the invention, the

styn parts being by weight unless otherwise stated, and the 9 4 methy|6.amin.7,3.bnm. violet. relationship of parts by weight to parts byvolume being carbostyril brown the same as that of the to the liter: l02-chloro-5-tri- 4-methyl-7-chloro6-amino orange fluoromethylcarbostyrilaniline EXAMPLE ll 4-methyl-6chloro-7-aminoscarlet carbostyril 36.1parts of the dyestuff, obtained by coupling [2 37 4'6 gime,hyl 7amimcarbo diazotised 2,5-dichloraniline with 2,3-hydroxyl naphthoicacid, are treated in 150 parts by volume of 13 -'F ortho-dichlorobenzenewith 10 parts of thionyl E2? y ChlOlidC f0! 3 hours at 110 to 120 C. Thedyestuff l4 4-methyl- 6-chloro-7-amino orange acid chloride thatcrystallizes as lustrous red needles 5 l 7 aminombo scarlet aftercooling is filtered off, washed with benzene and y then with etroleumether, and dried in vacuo at 40 to 16 4-methyl-6-methoxy-7-aminobrown P45 C. There are obtained about 34 parts of the "f' chloride corres ndinto 89 7 rcent of the theor tin zimmo'bemlc methym'mmowbmynl Scarlet r P0g P 6 acid methyl ester cal yield. 18 2- amino-benzoic 4-methyl-6-chloro-7-aminored 4.2 parts of 4-methyl-o-chloro-laminocarbostyril 191! fggg Hammmw red are dissolved in 150 parts by volume of N-methyl-pyrny rolidone, and 5.6 parts of the dyestuff acid chloride ob- 24-m;thyl-e-methox -7-aminored car styri tamed as described above areintroduced at room tem 21 Minimum red perature. The whole is stirred atroom temperature for acid ethyl alter curboatyrll 10 hours, and is thendiluted with 150 parts by volume 22 o e carbostyril violet of orthodichlorobenzene and heated to 149 to 145 C. 23 *chlomhmmwLmchYLlchlomhamim red After one hour the whole 15 filtered while hot,and dirphenylether. cm'bogtyfil washed with hot dichlorobenzene untilthe filtrate f g y i am e y es er running out is completely colorless.The filter residue 18 24 4 methyl 6 chlom 7 amino Scarlet then washedwith methanol and finally with hot water. uoromethyl-4'- carbostyril Bydrying the filter residue in vacuo at 90 to 100 C., gllowdlphcnyl 6 Clthere are obta1ned 9.8 parts, corresponding to 89 per- 25 a Scam, centof the theoretical yield, of a dark red powder. The carbostyril pigmentcol-responds to h f l 26 :y6;irilimethyl-7-aminocarbobordeaux 27 374-methyl-7-chloro-6-aminobrown-red 01 no COIIN /N CH carbostyril l l 282,4,5-trimethyl- 4-methyl-6-chloroJ-aminobordeaux N N O1 anilinecarbostyril 29 4-methyl-7-aminocarbostyril blue-red l 304-methoxy-3-ami- 4-methyl6-chloro-7-aminoruby red 01 UB3trifluoromethylacid carbostyril 3'-trifluor- By rolling this dyestuffinto polyvinyl chloride, there is metl1ylani1ide obtained a strongbluish red coloration of excellent &j; r' fasmess to 2 P and y 8 9fasmess to light so 32 4-methoxy-3- 4,6-dimethyl-7-aminocarboruby red Inthe following Table are given further pigment arn np nz i aci styr ldyestuffs that can be obtained in the manner described magm above, bycoupling the diazo-bases mentioned in 33 4-methyLB-aminoscarlet column Iwith 2,3-hydroxynaphthoic acids, converting qg 3 the resultingazo-dyestuff-carboxylic acids into their z fiz 7 acid chlorides, andcondensing the latter with the 34 4-methyl-7-chloro-6-amino redaminocarbostyrils mentioned in column ll. In column 35 i gy h 7 d iiiare given the tints of polyvinyl chloride films colored f i ammo re withthe pigments. 36 4-chloro-3-amino- 4-methyl-7-aminocarboorange benzoicacid 2',- styril TABLE 4"dichloroanilide 374,6-dimethyl7-aminocarboscarlet u m y" 384-methyl-6-chloro-7-aminoscarlet carbostynl l 2,5-dichloroani 394-chloro-3-amino- 4-methyl-7-chloro-6- scarlet line4-methyl-7-aminocarbostyril scarlet benzoic acid 2',- arninocarbostyril4,6- -dimethyl-7-aminocarbored-brown 4'-dichloranilide styril 3Lmethyl-fi-methoxyJ-aminored carbostyril n EXAMPLE 2.

18.8 parts of 4,6-dimethyl-7-aminocarbostyril are stirred in 250 partsby volume of N-methylpyrrolidone. 23.5 parts of 2,3-hydroxynaphthoicacid chloride are then introduced at room temperature. The temperatureis slowly raised to 40 C., and after a short time a clear solution isobtained. After about 1 hour the condensation product begins tocrystallize. The whole is stirred for 6 hours at room temperature, andit is then diluted with 250 parts by volume of methanol and filtered.The filter residue is washed with methanol and then with water. Afterdrying the residue in vacuo at 70 to 75 C., there are obtained 285parts, corresponding to 79.5 percent of the theoretical'yield, of thenaphthol component of the formula Analysis: Calculated: C=73.73 H=5.50N=7.8 1%

3.2 parts of 2,5-dichloroaniline are diazotised in known manner with 5parts by volume of hydrochloric acid of 30 percent strength and 5 partsby volume of a 4N-solution of sodium nitrite at 0 to 2 C. Thediazosolution is clarified by filtration, if necessary, and is made upto 200 parts by volume and adjusted to 0 C. After the addition of partsof crystalline sodium acetate, there is introduced dropwise, whilestirring, at to C a solution of 7.2 parts of the 2,3-hydroxynaphthoicacid arylide, obtained as described in the preceding paragraph, in 100parts by volume of dimethylformamide and 25 parts by volume of a 2N-solution of sodium hydroxide. In order to complete the coupling thewhole is stirred for 1 hour at 20 to 25 C and is then heated to 80 to 85C. The whole is filtered while hot, and the dyestuff is washed free fromsalt with hot water. After drying it in vacuo at 90 to 95 C, there areobtained 9.4 parts (corresponding to 88.7 percent of the theoreticalyield) of the dyestuff of the formula This pigment dyes syntheticplastics, such as polyvinyl N oonN-- -011 i chloride, or lacquers, redtints having very good fast- 2,3-hydroxynaphthoic acid chloride theaminocarbostyrils mentioned in Column II. In column III are given thetints produced with these pigments in polyvi- 6-amin0carb0styril EXAMPLE3.

20.85 pans of 4-methyl-6-chloro-7-aminocarbostyril are suspended in 200parts by volume of glacial acetic acid, and 9 parts of diketen areintroduced dropwise at 60 to 65 C., while stirring, in the course of 10minutes. When the addition is complete the mixture is heated for onehour at 90 to 95 C. The initially very fine white suspension changesinto a thick magma of handsome lustrous crystals. After being cooled toroom temperature the mixture is filtered with suction, and the filterresidue is washed first with acetic acid of 40 percent strength and thenwith water until the filtrate running out is neutral. By drying theresidue in vacuo at to C there are obtained 27.5 parts, corresponding to94 percent of the theoretical yield, of 4-methyl-6-chloro-7-acetoacetylamino-carbostyril in the form of lustrouscolorless needles which melt at 253 C with decomposition.

Analysis: Calculated: C=57.41 H=-4.45 Cl=l2. l4 N=9.58%

Found C=57.43 l-l=4.38 Cl=l2.09 N=9.6l%

17.25 parts of 4-chloro-2-nitraniline are diazotised in the usual mannerand the clear filtrate of the diazosolution is adjusted to a volume of400 parts and a temperature of 0 C. After the addition of 25 parts ofcrystalline sodium acetate, there is introduced dropwise, whilestirring, a solution of 29.5 parts of acetoacetic acid arylide, obtainedas described in the preceding paragraph in 150 parts by volume ofethanol, 20 parts of sodium hydroxide of 30 percent strength and 200parts of water. The whole is stirred for one hour at 20 to 25 C, thenheated for a short time at C, filtered, and the filter residue is washedfree from salt with hot water. By drying the residue at 90 to 95 C invacuo there are obtained 46 parts, corresponding to 96.6 percent of thetheoretical yield, of the dyestuff of the formula This dyestufi ispractically insoluble in the usual solvents. It dyes synthetic plasticsand lacquers greenish yellow tints of excellent fastness to migrationand light.

In the following Table are given further pigment dyestufi's which can beobtained in the manner described above by coupling the amines mentionedin column 1 with the aceto-acetyl derivatives obtained by O thepigments.

I II III condensing diketen with the arninocarbostyrils men l "311i"tioned in column II. In column III are given the tints of carbostyril yy polyvinyl chloride films colored with the pigments. 2 i Ye"ow nzi me 33,3'-dimethoxy-6,6'- yellow l 11 III dichlorobenzidine o 43,3'-dimethoxy- Orange benzidine 1 Z-nitroA-chloranrlrne4-methyl-6-methoxygreenish 5 3,3' dichlorobenzidine 4,6-dimethy reddish7-aminocarbostyril yellow acetoacetylamino yellow 2 4-methyl-7-chloro-6-yellow carbostyril aminocarbostyril 6 3,3',6,6'-tetrachloroyellow 3Z-nitroA-methylaniline 4-me hyl-7-amino yellow benzidine carbostyril 73,3'-dichlorobenzidine 4-methyl-7-chlororeddish 4 4,6-dimethyl-7-reddish o acetoaicetylaminoyellow aminocarbostyril yellow carbostyril 5Z-n tro-4-methoxyreddish 8 3,3'6,6'-tetrachloro Yellow aniline yellowbenzidine 6 2,5-dlmethoxy-aniline- 4-methyl-6-methoxy yellow 93,3'-dimethyl-6,6'- reddish 4-sulphonic acid anilide 7-aminocarbostyrildichlorobenzidine yellow 7 4-chloro-3aminobenzoic 4-methyl-6-chloro-7-greenish 3O 10 3,3'-dimethoxy-6,6'- yellow acid 2'-rr ethyl-5-aminocarbostyri yellow dichlorobenzidine chloranilide l l3,3'-dimethoxyorange 8 4,6-dimethyl-7- yellow b idi amino-carbostyril 94-chloro-3-aminobenzoic 4-rnethyl6-methoxyyellow acid 2'-chloro-5'-tri-7-aminocarbostyril fluoromethylanilide EXAMPLE 5.

65 parts of stabilized polyvinyl chloride, 35 parts of dioctyl phthalateand 0.2 part of the pigment obtained as described in paragraphs 1 and 2of Example 1 are mixed together and then rolled backwards and forwardson a two-roller calender for 7 minutes at 140 C. There is obtained abluish red film of very good fastness to light and migration.

What we claim is:

l. A monoazo-dyestuff pigment of the formula EXAMPLE 4.

4.21 parts of the coupling product of 1 mol of 40 tetrazotised3,3-dichlorobenzidine and 2 mols of diethylamine are stirred with 5.8parts of 4-methyl-6- methoxy-7-acetoacetyl-amino-carbostyril in 150parts by volume of glacial acetic acid, and the whole is heated to 100to 110 C. The whole is stirred at that temperature for 4 hours, thenfiltered while hot, and the separated pigment is washed with hotorthodichlorobenzene and then with methanol. After drying q n W it at 90to 95 C in vacuo there are obtained 6.8 parts, 1 corresponding to 87.2percent of the theoretical yield, N of the yellow pigment dyestuff ofthe formula 1% .7 I V X ICH: NH X2 ooH E o 0 Y -o 0 NH 110--NHCO-([3H-N=N NH 1 CH; 50 O Hie m which W represents chloro, bromo,fluoro, lower al- 1 kyl, lower alkoxy, carboethoxyphenoxy, phenoxy,chlorophenoxy, nitro or C lower carbalkoxy, U

represents hydrogen, methoxy, ethoxy, carbophenoxy, carboxamido, methyl,chloro, bromo, nitro or 1t dyes synthetic plastics, such as polyvinylchloride, trifluoromethyl, Vrepresents hydrogen, chloro, bromo, strongreddish yellow tints of very good fastness to methyl, nitro, methoxy, Ccarball-toxy, carbophenoxmlgratlon andllght. y, carboxamido, N-C alkylcarboxamido,

trifluoromethyl unsubstituted carboxylic phenylamido, substitutedcarboxylic phenylamido wherein the substituents are selected from thegroup consisting of chloro, methyl, phenyl and tn'fluoromethyl;sulfonamido, sulfonic ethylamido, sulfonic phenylamido, substitutedsulfonic phenylamido wherein the substituents are selected from thegroup consisting of chloro and trifluoromethyl, X represents hydrogen,lower alkyl or phenyl, X and X each represents hydrogen, chloro, loweralkyl, phenyl or lower alkoxy, or together with the two adjacent carbonatoms of the benzene ring which they occupy a further unsubstitutedbenzene ring and Y represents hydrogen, bromo, lower alkoxy, nitro orcyano and in which the NH- group is bound in the 6- or 7-position of theearbostyril radical.

2. The compound as claimed in claim 1 of the formu- 3. The compound asclaimed in claim 1 of the formu- 4. The compound as claimed in claim 1of the formu- 4 COCIIa l0 5. The compound as claimed in claim 1 of theformu- 6. The compound as claimed in claim 1 of the formuc m 3m -OONllq7. The im ound as claimed in claim 1 of the formu 3 3 UNITED STATESPATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,68%,792 DatedAugust 15, 1972 Inventor(s) WILLY MUELLER It is certified that errorappears in the above-identified patent and that said Letters Patent arehereby corrected as shown below:

Cover Page, after the Inventors and before "[22] insert ---Assignors toCIBA-GEIGY AG, Basie,

Switzerland---.

Signed and sealed this 16th day of April 197R.

(SEAL) I Attest:

EDI-IARD ILFLETCHER,JR. C. MARSHALL DANN Atte sting Officer Commissionerof Patents

2. The compound as claimed in claim 1 of the formula
 3. The compound asclaimed in claim 1 of the formula
 4. The compound as claimed in claim 1of the formula
 5. The compound as claimed in claim 1 of the formula 6.The compound as claimed in claim 1 of the formula
 7. The compound asclaimed in claim 1 of the formula